Composition of matter and process for obtaining same



Unite-13mm P rent- Y COMPOSITION OF MATTER AND PROCESS FOR OBTAININGSAME Joseph Cunder, East Orange, and Francis J. Licata, West Caldwell,NJ., assignors to Nopco Chemical Company, Harrison, N.J., a corporationof New Jersey No Drawing. Filed Feb. 21, 1958,-Ser. No. 716,547

6 Claims. (Cl. 260-18) The present invention relates to novel metallicsoap products. More particularly, the present invention re-' "lates tometallic soap products that have great utility in compositions such assanding sealers, lacquers and the ike.

Use of metal soaps in sanding sealers, lacquers and varnish compositionsis well known and has been practiced by the art for many years. Sandingsealers are lacquer type coatings which are primarily employed to sealporous surfaces such as wood and are designed to rials which are addedfor the purpose of bringing about dull or matte finishes are known asflatting agents. Well, known flatting agents are, for instance, metallicsoaps .such as zine stearate, zinc palmitate, calcium stearate andmagnesium stearate.

However, in order to use these various metallic soaps as additives tosanding sealers, lacquers and varnishes, it is necessary to first grindthem in order to disintegrate or break down the clusters of the soapinto their individual particles. Generally, the soaps are ground in thepresence of a hydrocarbon solvent or in the presence of a portion of thevehicle to which they are to be added. Pebble mills may be employed forgrinding and their use involves grinding periods for up to twenty.hours. Such grinding procedures involve unavoidably long periods of timeas well as involving the extra manipulative step plus .the necessarygrinding equipment. Also, in many instances, heat generated duringgrinding procedures may cause discoloration of the various soaps. It hasalso been found in the case of zinc soaps, particularly due to theirextreme fineness and' large surface area, that they contain a largevolume of air which in many instances during grinding becomesemulsified. This produces very rigid foams which cannot be poured out ofthe pebble mills.

Additionally, metallic soaps as presently employed bring aboutundesirable thickening of the vehicle when too high a concentration ofsoap is employed. Hence, the solids concentration is usually kept low toavoid this thickening, but, in many instances this results in filmshaving poor weathering qualities because of the small amount of metallicsoap present. These metallic soaps are, of course, known for theirwater-proofing properties. I Accordingly, it is an object of the presentinvention to obtain improved compositions of metallic soaps.

It is a further object to obtain improved metallic soaps in finelydivided form which are useful in sanding sealers, llacquers, varnishesand the like.

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It is another object to obtain improved metallic soaps in finely dividedform that are useful as flatting agents.

It is a still further object to prepare finely divided metallicsoapsusefulas additives 'to the aforementioned vehicles without the necessityof grinding the soaps in order to obtain them in finely dividedparticles.

A further object is to obtain improved compositions of metallic soapsthat may be used in increased quantities in organic vehicles such asvarnishes and lacquers, without detracting from the stability, color orfreely flowing properties of such vehicles and which may be added tosuch vehicles by simple mixing.

Further objects will become apparent from the detailed description givenhereinafter. It is-intended, however, that the detailed description andthe specific examples do not limit the invention, but merely indicatethe preferred embodiments of the invention since various changes andmodifications within the scope of the invention will become apparenttothose skilled in the art.

Theabove and other objects are accomplished in the following manner. -Ithas unexpectedly been discovered that when a water-soluble soap isprecipitated with a water-soluble zinc salt in the presence of an epoxyresin or ester thereof, to be described hereinafter, or when'a zinc soapis admixed with said epoxy resin or es'ter thereof, a product isobtained which is a uniform mixture of a zinc soap and resinor esterthereof and has the following unexpected characteristics. The product isin a finely divided state and after grinding to form optimum particlesize may be added directly to a vehicle without further mechanicalgrinding. It may be added in increased quantities to such vehicleswithout in any manner decreasing or affecting the fluidity of freelyflowing properties of the mixture which may be a sanding sealer, lacqueror varnish composition. These compositions are of good color and stableand moreover, because increased quantities of metallic soap may beincorporated therein, they napthyD-methane While suitable halohydrinsare epichlorohydrin, and dichlorohydrins such as 1,3 dichloro-Z- hydroxypropane and 1,2-dichloro-3-hydroxy propane.

These resins are prepared by heating the halohydrin and dihydric phenolfor several hours at elevated temperatures of e.g., 50 to C. Whenepichlorohydrin and a dihydric phenol are reacted, they may be presentin a ratio of from about one to two mols of epichlorohydrin per rnol ofdihydric phenol A base such as sodium or potassium hydroxide is alsopresent in an amount sufiicient to neutralize the acid formed duringreaction. Gen- I .erally an excess of base is present e.g., 1.1 to 1.3chemical equivalents of base per mol of epichlorohydrin.

-When epichlorohydrin and bis-(4-hy'droxyphenyl) 'dimethyl methane, alsoreferred to as bisphenol-A,'are reacted together, materials generallybelieved to have the structure I I i 3 are obtained where 'n representsthe extent of polymerizati'on. When the mol ratio of epichlorohydrin tophenol is 2:1, n is zero and the molecular weight is 340 accord- EpouResin (Shell M.1 C. Eppxide Av. Mole- Chemieal Co.) No. (Durrans Method)1 Equivalent cular Wt.

Liquid (at R.T. 175-210 350-400 Liquid (at RIP. .4 225-290 450 4050300-375 700 6446 450-525 900-1, 000 95405 870-1, 025 1 -1, 400 125432 1,650-2, 050 2, 900

It is of course understood .that the above epoxy resins are not the onlyepoxy resins that may be employed herein. They are merely exemplary ofthe various commercially available materials useful within the scope ofthis invention since other epoxy resins are obtainable when, in lieu ofthe aforementioned polyhydroxy aryl compounds, other polyhyrodxymaterials such as ethylene glycol, diethylene .glycol, glycerine, etc.are used.

It is to be understood that the preparation of the epoxy resins andesters thereof are not part of this invention and the invention is notlimited to resins obtained by any one particular method. Additionally,other resins such as epoxy resin esters have been found to be suitablein the present invention. They are prepared by reacting the epoxy resinwith a fatty acid to bring aboutesterification -of the resin. Suitablefatty acids are saturated and unsaturated nionocarboxylic fatty acidshaving from 8 to 22 carbon atoms such as caprylic, ethyl hexoic,palmitic, stearic, arachidic, behenic, oleic, linoleic acids etc., andmixtures thereof as Well as naturally occurring sources thereof, e.g.,soybean fatty acids, linseed fatty acids, castor fatty acids, coconutfatty acids, etc.

To prepare thenovel flatting agents, a fatty acid is first saponifiedalone, or in the presence of the resin which is uniformly dispersedthroughout the solution. Any suitable saturated fatty acid may be usedas the starting material i.e., saturated aliphatic monocarboxylic acidshaving from about 8 to 22 carbon atoms such as palmitic, s'tearic,arachidic, behenic, caprylic or ethyl .hexoic acids and their mixtures,fatty acids obtained by splitting g'lycerides and mixtures thereof suchas tallow, hydrogenated fish oils, e.g., hydrogenated sardine oil,hydrogenated vegetable oils e.g., hydrogenated soy bean oil,hydrogenated castor oil, hydrogenated cottonseed oil and hydrogenatedcoconut oil.

Processes for the conversion of fatty acids or glycerides if such areused, into water-soluble soaps using an alkali are well known in theart. Generally, saponification is accomplished by reacting the fattyacid or glyceride with a base-such as sodium, potassiumor ammoniumhydroxide in the presence of water. Since water-solublesoaps producedbyany of the prior art processes are fully suited for use in the presentinvention, nothing herein should be construed as limiting the presentinvention to the use of soaps obtained by any one particular method.

Thereafter, a water soluble zinc salt is added to the resultingWater-soluble soap solution which also contains the epoxy resin. If theresin was not present during saponification, it may be added prior to orwith the addition of the water-soluble zinc salt. This addition bringsabout precipitation of the sbapas a zinc soap containing the resinuniformly dispersed throughout the soap. Al-

ternatively, the zinc salt may be added to a solution or dispersion ofthe water-soluble soap in the absence of the resin which may besubsequently admixed with the resulting Zinc soap.

The quantity of zinc salt employed to accomplish precipit'a'tion shouldbe at least sufficient to react with all of the water-soluble soappresent. While the use of a stoichiometrically equivalent quantity ofzinc salt solution should obviate the possibility that any water-solublesoap will be occluded in the precipitated product, an excess quantitycan be and is at times preferably employed. Suitable salts are zincsulfate, zinc chloride, zinc acetate, etc.

Precipitation is accomplished by adding a heated aqueous solution of thewater-soluble zinc salt to the solution or dispersion 'of the soap withor without the presence of the resin. If desired, this sequence can bereversed. The zinc salts previously recited are not limiting since otherzinc salts may be used provided they are soluble in water at thetemperature which they are to be used and provided further that thesesalts will form water-insoluble compounds with the water-soluble soaps.Generally the solution of the metal salt precipitant contains from 5% to40% by weight of zinc salt. Preferably about 20% zinc salt solutions areused. However, the concentration of the salt solution has little effect,if any, upon the precipitated composition. The salt solution when addedis usually at an elevated temperature e.g., from about 50 C. to about C.and the soap solution may likewise be at the same elevated temperatures.

After the desired composition has been precipitated, it can be separatedfrom the aqueous solution in which it is dispersed by any convenientmeans. Usually, this step is accomplished by passing the dispersionthrough a filter. The filtered product is subsequently washed severaltimes in water to remove residual water-soluble salts present.

The washing step is ordinarily carried out in water heated to atemperature of from about 40 C. to about 70 C. After washing, theproduct is dried, generally in an oven heated to a temperature of fromabout F. to F., and subsequently ground by appropriate means to obtainoptimum particle size. If the zinc soap was obtained in the absence ofthe resin, such may now be added by any convenient mixing means, e.g.,hammer type mill. The resulting product which, as stated before, is auniform mixture of a zinc soap and resin or ester thereof, althoughinsoluble and not dispersible in water, is highly dispersible in organicsolvents and other organic vehicles used in e.g., sanding sealer,lacquer or varnish compositions. As aforesaid, the addition of the novelproducts of the present invention to these solvents or vehicles isaccomplished by simple mixing without resorting to grinding and theseproducts may be present in amounts not heretofore possible to employ.

The quantity of epoxy .resin or ester thereof may vary and may be fromabout /2% to 20% by weight based upon the Weight of the fatty acid used.Prefer-ably 5% by weight based upon the weight of the fatty acid isused. Additionally, the solid composition may contain in minor amountsother constituents such as plasticizers, softeners, pigments, dyes andthe like.

Generally, when the novel products described herein are employed asflatting agents, they may be present in a lacquer in an amount o'f'from/2.% to 10% by weight of the lacquer. If they are to be employed insanding sealers, they may be also present in an amount of from /2% to10% by weight of the vehicle. If desired, however, up "to 25% of thesenovel soaps may be satisfactorily employed in the various vehicles.

For a fuller understanding of the nature and objects of the presentinvention, reference may'be made to the following examples which aregiven merely to illustrate the invention and are not to be construed in:a :limiting sense, all parts given being by weight.

i Example 7 950 parts of stearic acid and 50 parts'of Shell Epon Resin864 were melted together in the presence of 2000 parts of water at atemperature of 80 C. to 95 C. Thereafter 157 parts of dry sodiumhydroxide dissolved in water to form a 50% by weight solution were addedto the molten aqueous mixture of stearic acid and resin in order tosaponify the acid. The resulting soap, resin mixture was diluted withwater to form a 6% by weight concentration thereof based on the weightof the soap. To this solution, 375 parts of zinc sulfate monohydratedissolved in water to form a 20% by weight solution of zinc sulfatemonohydrate were slowly added during one hour to bring aboutprecipitation of the sodium stearate soap as zinc stearate containingthe resin uniformly dispersed throughout the zinc stearate. This wasaccomplished at a temperature of 80 to 85 C. The resulting precipitatewhich comprised a mixture of zinc stearate and resin was filtered offfrom the mother liquor and washed free of sulfates. The precipitate wasdried at 140 F. and ground through a ,6 inch screen.

The following data were determined upon analysis of the composition ofExample I, all percents being by weight.

Example II To illustrate the use-of our novel metal .soaps as fiattingagents, 1.4 parts of the product of Example I were stirred into 98.6parts of a lacquer referred to as C.M.L. XElSlO lacquer, a product ofthe Coating Materials Laboratory, Belleville, New Jersey. No grinding ofthe soap into the vehicle was carried out. The resulting product was ahomogeneous dispersion. A portion was applied to a glass plate and theresulting film was found to be-smooth with a minimum of agglomerations,i.e., it compared favorably with films prepared from lacquers having theflatting agent ground in e.g., with a pebble mill.

The C.M.L. lacquer was prepared as follows. First, two mixes wereprepared. Mix A contained 100 parts by weight of one-half secondnitrocellulose and 60 parts by weight of modified maleic resin (Arochem520 having an acid number of 25-35 and a melting point of l40-145 C.).Mix B contained 15 parts by weight ethanol, 50 parts by weight tolueneand 35 .parts by weight butyl acetate. Then the final composition wasmade by mixing together 20 parts by weight of Mix A with 80, parts byweight of Mix B.

Of course, lacquers containing other film formers besides nitrocellulosemay be used such as cellulose acetate and synthetic resins such asurea-formaldehyde resin or alkyd resins.

Example III 95 parts of double pressed stearic acid and 5 parts of ShellEpon Resin 1001 were melted together in the presence of 200 parts ofwater at a temperature of 80 to 95 C. 15.7 parts of dry sodiumhydroxide, dissolved in 15.7 parts of water were added to the moltenstearic acid, resin mixture in order to saponify the acid. The resultingsoap, resin mixture was diluted to 2000 parts of water to form about 5%concentration thereof based on the weight of the soap. To this solution37.5 parts of zinc sulfate monohydrate dissolved in water to form a 20%by weight solution of zinc sulfate monohydrate were slowly added duringone hour to precipitate the sodium stearate soap as zinc stearatecontaining the resin uniformly dispersed throughout the zinc stearate.This was accomplished at a temperature of 80 to 85 C. The resultingprecipitate which comprised a mixture of zinc Example IV 95 parts ofdouble pressed stearic acid and 5 parts of Shell Epon Resin 828 weremelted together in the presence of 200 parts of water at a temperatureofto 95 C. 15.7 parts of dry sodium hydroxide, dissolved in 15.7 parts ofwater were added to the molten stearic acid, resin mixture in order tosaponify the acid. The resulting soap, resin mixture was diluted to 2000parts of water to form about 5% concentration thereof based on theweight of the soap. To this solution 37.5 parts of zinc sulfatemonohydrate dissolved in water to form a 20% by weight solution of zincsulfate monohydrate were slowly added during one hour to precipitate thesodium stearate soap as zinc stearate containing the resin uniformlydispersed throughout the zinc stearate. This was accomplished at atemperature of 80 to C. The resulting precipitate which comprised amixture of zinc stearate and resin was filtered off from the motherliquor and washed free of sulfates. The precipitate was dried at 140 F.and ground through a ,4 inch screen.

Example V parts of double pressed stearic acid and 5 parts of Shell EponResin 1004 were melted together in the presence of 200 parts of water ata temperature of 8 0 tu 95 C. 15.7 parts of dry sodium hydroxide,dissolved in 15.7 parts of water were added to the molten stearic acid,resin mixture in order to saponify the acid. The resulting soap, resinmixture was diluted to 2000 parts ,of water to form about 5%concentration thereof based on the weight of the soap. To this solution37.5 parts of zinc sulfate monohydrate dissolved in water to form a 20%by weight solution of zinc sulfate monohydrate were slowly added duringone hour to precipitate the sodium stearate soap as zinc stearatecontaining the resin uniformly dispersed throughout the zinc stearate.This was accomplished at a temperature of 80 to 85 C. The resultingprecipitate which comprised a mixture of zinc stearate and resin wasfiltered oif from the mother liquor and washed free of sulfates. Theprecipitate was dried at F. and ground through a $4 inch screen.

0 Example VI 99 parts of double pressed stearic acid and 1 part of ShellEpon Resin 1001 were melted together in the presence of 200 parts ofwater at a temperature of 80 to 95 C. 15.7 parts of dry sodiumhydroxide, dissolved in 15.7 parts of water were added to the moltenstearic acid, resin mixture in order to saponify the acid. The resultingsoap, resin mixture was diluted to 2000 parts of water to form about 5%concentration thereof based on the weight of the soap. To this solution37.5 parts of zinc sulfatemonohydrate dissolved in water to form a 20%by weight solution of zinc sulfate monohydrate were slowly added duringone hour to precipitate the sodium stearate soap as zinc stearatecontaining the resin uniformly dispersed throughout the zinc stearate.This was accomplished at a temperature of 80 to 85 C. The resultingprecipitate which comprised a mixture of zinc stearate and resin wasfiltered off from the mother liquor and washed free of sulfates. Theprecipitate was dried at 140 F. and ground through a %.;-inch screen.

Example VII pressed stearic acid and 3 parts of 7 on the weight of thesoap. To this solution 37.5 parts ofzinc sulfate monohydrate dissolvedin water to form a 20% by weight solution of the zinc sulfatemonohydrate were slowly added during one hour to precipitate the sodiumstearate soap as zinc stearate containing the resin uniformly dispersedthroughout the zinc stearate. This was accomplished at a temperature of80 to 85 C. The resulting precipitate which comprised a mixture of zincstearate and resin was filtered off from the mother liquor and washedfree of sulfates. The precipitate was dried at 140 F. and ground througha & inch screen.

Example .VIII

990 parts of double pressed stearic acid and 10 parts of Shell EponResin 828 were melted together in the presence of 2000 parts of water ata temperature of 80 to 95 C. 157 parts of dry sodium hydroxide,dissolved in 157 parts of Water were added to the molten stearic acid,resin mixture in order to saponify the acid. The resulting soap, resinmixture was diluted to 20,000 parts of water to form about 5%concentration'thereof based on the weight of the soap. To this solution37. parts of zinc sulfate monohydrate dissolved in water to form a 20%by weight solution of zinc sulfate monohydrate were slowly added-duringone hour to precipitate the sodium stearate soap as zinc stearatecontaining the resin uniformly dispersed throughout the zinc stearate.This was accomplished at a temperature of 80 to 85 C. The resultingprecipitate which comprised a mixture of zinc stearate and resin wasfiltered 01f from the mother liquor and washed free of sulfates. Theprecipitate was .dried at 140 F. and ground through a inch screen.

Example IX 90 parts of double pressed stearic :acid along with parts ofShell Epon Resin 1001 were melted together in the presence of 200 partsof water at a temperature of 80 to 95 C. 15.7 parts of dry sodiumhydroxide, dissolved in 15.7 parts of water'were added to the moltenstearic acid, .resin mixture in order to saponify the acid. Theresulting soap, resin mixture was diluted to 2000 parts of water to formabout 5% concentration thereof based on the weight of the soap. To thissolution 37.5 parts of zinc sulfate vmonohydrate were slowly addedduring one hour to precipitate the sodium stearate soap as zinc stearatecontaining the resin uniformly dispersed throughout the zinc stearate.This was "accomplished at a temperature of 80 to 85 C. The resultingprecipitate which comprised a mixture of 'zinc stearate and resin wasfiltered off fromthe mother liquor and washed free of sulfates. Theprecipitate was dried at v140 and ground through a & inch screen.

Example X solution of zinc sulfate monohydrate was prepared from 37.5parts of zinc sulfate monohydrate. One third of this zinc sulfatesolution was added to the soap solution to bring about partialprecipitation. The temperature of the soap solution was maintained atabout 210 F. Thereafter, 5 parts of an ester of Shell Epon Resin 1001and stearic acid having an acid value of 20 was heated to about 210 andthen slowly poured into the partially precipitated soap to effect auniform dispersion of the resin. Finally the remainder of the zincsulfate solution was added to complete precipitation at the sametemperature. The precipitated material which comprised a mixture of zincstearate and resin was filtered oif from the mother liquor and washedfree of sulfates. It was then dried at F. and ground through a ,4 inchscreen.

Having described our invention what we claim as new and desire to secureby Letters Patent is:

1. A composition of matter comprising in admixture 1) zinc stearate and(2) a resin selected from the group consisting of an epoxy resin andesters thereof, said resin being present in an amount of from about /2%to 20% by weightbased upon the weight of stearic acid from which :saidzinc stearate is derived.

2. A composition .of matter comprising in admixture (1) zinc stearateand (2) a resin selected from the group consisting of a resinous epoxidewhich is a polyetherderivative of a dihydroxy aryl compound havingalternating aliphatic chains and aromatic nuclei united through otheroxygen and being free from functional groups other than epoxy andhydroxy groups and esters thereof, said resin being present in an amountof from about /2% to 20% by weight based upon the weight of stearie acidfrom which said zinc stearate is derived.

3. A composition of matter compr ing in admixture, (1 i t a a n n pox inwh ch is a densation polymer of epichlorohydrin and ,p,p-dihydroxycliphenyl dimethylmethane having a melting point of about 40 to 50 C.,an epoxide equivalent of about 300 to 3175 and an average molecularweight of about 700, said resin being present in an amountof about /2%to 20% by weight based upon the weight of stearic acid from which saidzinc stearate is derived.

4. A composition of claim 3 in which said resin is present in an amountof about 5% by weight based upon the weight of stearic acid from whichsaid zinc stearate is derived.

-5. A freely flowing liquid c mposition comprising a lacquer and in anamount of from about 12% to 25% by weight thereof, the composition ofclaim :1.

6. A freely flowing liquid composition comprising a lacquer and in anamount of from about /2% to 25% by weight thereof, the composition ofclaim 3 Payne: Organic Coating Fechnology, vol. 1, pages 429-30, JohnWiley.& Sons, Inc,, .N.Y., .1954.

1. A COMPOSITION OF MATTER COMPRISING IN ADMIXTURE (1) ZINC STEARATE AND(2) A RESIN SELECTED FROM THE GROUP CONSISTING OF AN EPOXY RESIN ANDESTERS THEREOF, SAID RESIN BEING PRESENT IN AN AMOUNT OF FROM ABOUT 1/2%TO 20% BY WEIGHT BASED UPON THE WEIGHT OF STEARIC ACID FROM WHICH SAIDZINC STEARATE IS DERIVED.